CN106410161A - Composite microsphere negative electrode material with core-shell structure, preparation method and application of composite microsphere negative electrode material - Google Patents
Composite microsphere negative electrode material with core-shell structure, preparation method and application of composite microsphere negative electrode material Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
The invention relates to the technical field of composite negative materials for batteries and discloses a composite microsphere (Li1.1V0.9O2/C) negative electrode material with a core-shell structure and a preparation method and an application of the composite microsphere negative electrode material. Li1.1V0.9O2 microspheres are utilized as core bodies for the composite microsphere negative electrode material, amorphous carbon is utilized as a matrix of a shell layer, and nanoscale Li1.1V0.9O2 granules are uniformly distributed in the matrix in an embedded manner. The preparation method includes the steps of dissolving lithium resources, vanadium resources and an adjuvant in absolute ethyl alcohol, and grinding; taking out a colloidal mixture obtaining from grinding, placing the colloidal mixture in an open container, and evaporating and drying to obtain a precursor; subjecting the precursor to low-temperature carbonization and high-temperature composition sequentially in an inert or reducing atmosphere so as to obtain the composite microsphere (Li1.1V0.9O2/C) negative electrode material, wherein, the molar ratio of the lithium resources to vanadium resources (Li to V) is 1.1:0.9. When the composite negative material is charged or discharged by the electric current density of 30mA/g, the first discharge capacity at the room temperature is larger than 900mAh/g, the first charge and discharge efficiencies are larger than 85%, and the capacity retention ratio remains above 90% after 500 times of cycles.
Description
Technical field
The present invention relates to the technical field of battery cathode composite material, more particularly to a kind of, there is nucleocapsid structure
Li1.1V0.9O2/ C micro-sphere compound anode material and its preparation method and application.
Background technology
Lithium ion battery as a kind of novel green accumulator, with its running voltage high, lightweight, specific energy is big, certainly put
Electric rate is little, have extended cycle life, memory-less effect, non-environmental-pollution the advantages of, in the secondary cell that replacement progressively is traditional
As lead-acid battery, Ni-Cr battery, Ni-MH battery position, become video camera, mobile phone, notebook computer and portable survey
The miniaturization electronic installation such as measuring appratus and the ideal source of environmental-protecting type electric automobile.Lithium-ion-power cell industry is promoted to send out
Exhibition, can drive a huge pollution-free industry cluster to emerge rapidly, have great strategic significance and pulling production to national economy.
Lithium-ion-power cell belongs to energy-conservation and new energy field simultaneously, meets the demand for development of national policy.For a long time, the U.S. props up
Hold the development that multiple National Laboratories undertake automobile-used lithium ion battery together with enterprise.European Union has then formulated high-energy-density storage
The development plan of battery, phasic results are born in not pregnancy ceased.Japan is the country of lithium-ion-power cell technological precedence, from
Nineteen ninety Japan succeed in developing lithium ion battery and put on market since, because its unique performance at home and abroad defines one lithium
Ion battery research boom.Lithium ion battery be develop in current chargeable battery very fast, application prospect very wide one
Plant high-energy secondary battery.
The lithium ion battery negative material of commercialization at present is mainly material with carbon element, shows excellent cyclical stability.But
The actual specific capacity closely theoretical specific capacity of carbon negative pole material, the potentiality improving its specific capacity further are substantially impossible,
In addition consume active material during initial charge and electrolyte forms solid electrolyte interface film and affects the performance of battery, and
There is potential safety hazard.Therefore, in order to improve the performance of lithium ion battery, find one kind and can substitute carbon negative pole material, and have
The novel cathode material for lithium ion battery of height ratio capacity becomes necessary, the urgent demand of lithium ion battery industry.Lithium transition gold
Belong to oxide and have potential development space for lithium ion battery negative material, lithium transition-metal oxide is used for lithium-ion electric
The research of pond negative material includes LiSnO, LiTiO, LiVO etc., wherein Sn oxide capacity highest, but its first cycle
The problems such as capacitance loss is serious constrains its Practical Progress, Li4Ti5O12It is structure highly stable famous " zero change material ",
Also obtain larger concern at present, but its potential plateau is higher so that the use in some fields is restricted.
Content of the invention
The technical problem to be solved in the present invention is the defect overcoming prior art, provides a kind of specific capacity height, cycle performance
Excellent, Stability Analysis of Structures, the eco-friendly Li with nucleocapsid structure1.1V0.9O2/ C micro-sphere compound anode material.
Another object of the present invention is to providing a kind of Li with nucleocapsid structure1.1V0.9O2/ C micro-sphere compound anode material
Preparation method.
Another object of the present invention is to providing a kind of Li with nucleocapsid structure1.1V0.9O2/ C micro-sphere compound anode material
Application.
The purpose of the present invention is achieved through the following technical solutions：
A kind of Li with nucleocapsid structure1.1V0.9O2/ C micro-sphere compound anode material, described composite negative pole material with
Li1.1V0.9O2Microsphere is nucleome；Shell, with amorphous carbon as matrix, is uniformly distributed and embedded into a nanometer Li in described matrix1.1V0.9O2
Granule.
Preferably, with the gross weight of composite negative pole material finally to be obtained as standard, Li1.1V0.9O2Content be 90～
99.9 weight %, the content of amorphous carbon is 0.1～10 weight %.
Preferably, described Li1.1V0.9O2A diameter of 0.5～2 μm of microsphere, shell thickness is 100～150nm, described
Li1.1V0.9O2The particle diameter of/C microsphere is 0.6～2.5 μm.
Preferably, described amorphous carbon has meso-hole structure；Described nanometer Li1.1V0.9O2The particle diameter of granule be 30～
50nm.
A kind of described Li with nucleocapsid structure1.1V0.9O2The preparation method of/C micro-sphere compound anode material, including following
Step：Will be by element Li：The mol ratio of V is 1.1:0.9 lithium source and vanadium source, and adjuvant is dissolved in dehydrated alcohol, then
It is ground；It is put into grinding the colloidal mixture taking-up obtaining in open-top receptacle, after being evaporated drying, obtain presoma；Will
Described presoma carries out low-temperature carbonization, high-temperature nuclei in inertia or reducing atmosphere successively, obtain described in there is nucleocapsid structure
Li1.1V0.9O2/ C micro-sphere compound anode material.
In the preparation process of composite negative pole material of the present invention, adjuvant plays the effect of following several respects：First, it is auxiliary
Auxiliary agent can stop growing up of crystal grain by pyrogenous origin amorphous carbon, and reduces Li1.1V0.9O2The particle diameter of microsphere, promotees simultaneously
Make a nanometer Li1.1V0.9O2Even particulate dispersion is in matrix；Second, adjuvant can increase the viscosity of liquid phase mixture, make
Li1.1V0.9O2Microsphere and nanometer Li1.1V0.9O2Granule is stable in the mixture, does not deposit；Third, being formed in colloidal mixture
With Li1.1V0.9O2Microsphere is core, bonds agraphitic carbon and nanometer Li with adjuvant1.1V0.9O2Granule is the nucleocapsid structure of shell
Glueballs；Fourth, forming amorphous mesoporous carbon structure after adjuvant carbonization, form a kind of Li with nucleocapsid structure1.1V0.9O2/C
Micro-sphere compound anode material.
Preferably, described lithium source is Li2CO3、LiNO3、CH3COOLi、LiOH、Li2C2O4One or more of；Described
Vanadium source is VO2、V2O3、V2O5、V4O7、NH4VO3One or more of.
Preferably, described adjuvant be polyvinyl alcohol, ethylene glycol, Polyethylene Glycol, citric acid, glucose, sucrose, the third three
One or more of alcohol, epoxy resin.
Preferably, described be ground to ball milling, ball milling jitter time be 2～4h, rotating speed be 250～300r/min.
Preferably, at 50 DEG C～90 DEG C, evaporation time is 24～48h to the temperature control of evaporation；The temperature of described low-temperature carbonization
Degree controls at 400 DEG C～600 DEG C, and carbonization time is 2～5h；The temperature control of described high-temperature nuclei at 950 DEG C～1100 DEG C, instead
It is 6～12h between seasonable.
A kind of described Li with nucleocapsid structure1.1V0.9O2/ C micro-sphere compound anode material answering in preparation battery cathode
With.
With respect to prior art, the present invention has the advantages that：
The present invention is the precursor adding adjuvant as agraphitic carbon, in Li after carbonization1.1V0.9O2The outer layer shape of microsphere
Become the shell of good meso-hole structure, both become a nanometer Li1.1V0.9O2The matrix of particle bearing, becomes Li again1.1V0.9O2Microsphere
The long-pending cushion expanding, thus be maintained at Li in charge and discharge process1.1V0.9O2The constancy of volume of/C micro-sphere compound anode material, also
The diffusion length that electrolyte shortens lithium ion can be adsorbed, be conducive to the quick diffusion of electronics.
The micro-sphere compound anode material of nucleocapsid structure of the present invention is with respect to the composite negative pole material coating only with amorphous carbon
For material, improve the frame mode of shell, in shell, embedded in a nanometer Li1.1V0.9O2Granule improves specific capacity.
The present invention is with Li1.1V0.9O2Microsphere is core, to embed nanometer Li1.1V0.9O2The amorphous carbon of granule is the compound of shell
In 30mA/g electric current density discharge and recharge, under room temperature, first discharge specific capacity is more than 900mAh/g, first charge-discharge to negative material
Efficiency is more than 85%, and after 500 circulations, capability retention is more than 90%.
The preparation method process is simple of the present invention, easily operation, cost are relatively low, for obtaining the nucleocapsid knot of above-mentioned function admirable
Structure Li1.1V0.9O2/ C micro-sphere compound anode material provides a kind of effective way.
Brief description
Fig. 1 is the Li with nucleocapsid structure1.1V0.9O2The XRD diffraction pattern of/C micro-sphere compound anode material；
Fig. 2 is the Li with nucleocapsid structure1.1V0.9O2The SEM figure of 40000 times of the amplification of/C micro-sphere compound anode material.
Specific embodiment
Further illustrate the present invention with reference to specific embodiment.Unless stated otherwise, adopt in the embodiment of the present invention
Raw material and method are the conventional commercial raw material in this area and conventional use of method.
The present invention has the Li of nucleocapsid structure1.1V0.9O2The preparation method of/C micro-sphere compound anode material, mainly include with
Lower step：
Comprise the following steps：Will be by element Li：The mol ratio of V is 1.1:0.9 lithium source and vanadium source, and adjuvant is dissolved in
In dehydrated alcohol, then it is ground；It is put into grinding the colloidal mixture taking-up obtaining in open-top receptacle, be evaporated drying
After obtain presoma；Described presoma is carried out low-temperature carbonization, high-temperature nuclei in inertia or reducing atmosphere successively, obtains institute
State the Li with nucleocapsid structure1.1V0.9O2/ C micro-sphere compound anode material.
More specifically：
S1. lithium source and vanadium source are pressed element Li：V mol ratio is 1.1：0.9 weighs mixing, and lithium vanadium mixture and adjuvant are pressed
Mass ratio 80：20 are dissolved in dehydrated alcohol, be added in ball grinder grind, ball milling jitter time be 2～4h, rotating speed be 250～
300r/min.Then, take out colloidal mixture to be put in open glass ware, 50 DEG C～90 DEG C evaporation drying 24～48h, before obtaining
Drive body.
S2. the presoma obtaining is carried out low-temperature carbonization, low-temperature carbonization process is carried out in inertia or reducing atmosphere, low
Warm carburizing temperature controls at 400 DEG C～600 DEG C, and carbonization time is 2～5h.
S3. the product after low-temperature carbonization is carried out high-temperature nuclei, high-temperature nuclei process is also in inertia or reducing atmosphere
Carry out, synthesis temperature controls at 950 DEG C～1100 DEG C, the response time is 6～12h.Final acquisition has nucleocapsid structure
Li1.1V0.9O2/ C micro-sphere compound anode material.
This composite negative pole material is with Li1.1V0.9O2Microsphere is nucleome；Shell, with amorphous carbon as matrix, uniformly divides in matrix
Cloth embedded nanometer Li1.1V0.9O2Granule.With the gross weight of composite negative pole material finally to be obtained as standard, Li1.1V0.9O2's
Content is 90～99.9 weight %, and the content of amorphous carbon is 0.1～10 weight %.Li1.1V0.9O2A diameter of the 0.5 of microsphere～
2 μm, shell thickness is 100～150nm, Li1.1V0.9O2The particle diameter of/C microsphere is 0.6～2.5 μm.Amorphous carbon has mesoporous knot
Structure；Nanometer Li1.1V0.9O2The particle diameter of granule is 30～50nm.
The invention will be further described by the following examples.
Embodiment 1
There is the Li of nucleocapsid structure1.1V0.9O2The preparation method of/C micro-sphere compound anode material, comprises the following steps：
By synthesis material lithium vanadium mixture (CH3COOLi、V2O3) and polyvinyl alcohol in mass ratio be 80：20 weigh gross mass
40 grams, lithium vanadium mixture is Li：V mol ratio 1.1：0.9 CH3COOLi、V2O332 grams of mixture, is dissolved in 40 milliliters of anhydrous second
In alcohol, and add 8 grams of polyvinyl alcohol, so that reactant is fully dispersed in ethanol.With 300 revs/min on planetary ball mill
Rotating speed ball milling obtained colloidal mixture after 4 hours, and colloidal mixture is put in open glass ware, and 80 DEG C of evaporations are dried 48 hours
After obtain presoma.Then by this presoma in argon gas atmosphere 500 DEG C of carbonizations of low temperature 3 hours, then close at 1050 DEG C of high temperature
Become 8 hours, naturally cool to room temperature, take out, final acquisition has nucleocapsid structure Li1.1V0.9O2/ C micro-sphere compound anode material.
The above-mentioned composite negative pole material preparing is with Li1.1V0.9O2Microsphere is nucleome；Shell with amorphous carbon as matrix,
It is uniformly distributed and embedded into a nanometer Li in matrix1.1V0.9O2Granule.The preparation of electrode and performance test：By above-mentioned prepare answer
Close negative material, acetylene black and PVDF in mass ratio 80:10:10 in NMP mix homogeneously, be coated on Copper Foil be electrode film,
Metal lithium sheet is to electrode, and Celgard2400 is barrier film, 1mol L-1LiPF6/ EC+DMC is electrolyte, full of Ar glove
It is assembled into button cell in case.Constant current charge-discharge test is carried out using Arbin BT-2000 electrochemical test.Discharge and recharge electricity
Pressure scope is 2.0～0.01V, and electric current density is 30mA g-1.Electrochemical property test the results are shown in Table 1.
The composite negative pole material that the present embodiment prepares XRD diffraction pattern and the SEM figure amplifying 40000 times, such as Fig. 1
With shown in Fig. 2.
Embodiment 2
There is the Li of nucleocapsid structure1.1V0.9O2The preparation method of/C micro-sphere compound anode material, comprises the following steps：
By synthesis material lithium vanadium mixture (CH3COOLi、V2O5) and polyvinyl alcohol in mass ratio be 80：20 weigh gross mass
40 grams, lithium vanadium mixture is Li：V mol ratio 1.1：0.9 CH3COOLi、V2O532 grams of mixture, is dissolved in 40 milliliters of anhydrous second
Alcohol, and add 8 grams of polyvinyl alcohol, makes reactant be fully dispersed in ethanol, with 300 revs/min turn on planetary ball mill
Fast ball milling obtained colloidal mixture after 4 hours, and colloidal mixture is put in open glass ware, after 80 DEG C of evaporations are dried 36 hours
Obtain presoma.Then by this presoma in argon gas atmosphere 600 DEG C of carbonizations of low temperature 2 hours, then synthesize at 1100 DEG C of high temperature
10 hours, naturally cool to room temperature, take out, final acquisition has nucleocapsid structure Li1.1V0.9O2/ C micro-sphere compound anode material.
The preparation of above-mentioned composite negative pole material electrode and performance test are same as Example 1, electrochemical property test result
It is shown in Table 1.
Embodiment 3
There is the Li of nucleocapsid structure1.1V0.9O2The preparation method of/C micro-sphere compound anode material, comprises the following steps：
By synthesis material lithium vanadium mixture (Li2CO3、V2O3) and Polyethylene Glycol in mass ratio be 80：20 weigh gross mass 40
Gram, lithium vanadium mixture is Li：V mol ratio 1.1：0.9 Li2CO3、V2O332 grams of mixture, is dissolved in 40 milliliters of dehydrated alcohol,
And add 8 grams of Polyethylene Glycol, so that reactant is fully dispersed in ethanol, with 280 revs/min of rotating speed ball on planetary ball mill
Mill obtained colloidal mixture after 3 hours, and colloidal mixture is put in open glass ware, and 70 DEG C of evaporations obtain after drying 24 hours
Presoma.Then by this presoma in argon gas atmosphere 400 DEG C of carbonizations of low temperature 4 hours, then synthesis 12 is little at 950 DEG C of high temperature
When, naturally cool to room temperature, take out, final acquisition has nucleocapsid structure Li1.1V0.9O2/ C micro-sphere compound anode material.
The preparation of above-mentioned composite negative pole material electrode and performance test are same as Example 1, electrochemical property test result
It is shown in Table 1.
Embodiment 4
There is the Li of nucleocapsid structure1.1V0.9O2The preparation method of/C micro-sphere compound anode material, comprises the following steps：
By synthesis material lithium vanadium mixture (Li2CO3、V2O5) and polyvinyl alcohol in mass ratio be 80：20 weigh gross mass 40
Gram, lithium vanadium mixture is Li：V mol ratio 1.1：0.9 Li2CO3、V2O532 grams of mixture, is dissolved in 40 milliliters of dehydrated alcohol,
And add 8 grams of polyvinyl alcohol, so that reactant is fully dispersed in ethanol, with 300 revs/min of rotating speed ball on planetary ball mill
Mill obtained colloidal mixture after 4 hours, and colloidal mixture is put in open glass ware, and 80 DEG C of evaporations obtain after drying 36 hours
Presoma.Then by this presoma in argon gas atmosphere 500 DEG C of carbonizations of low temperature 3 hours, then synthesis 10 is little at 1000 DEG C of high temperature
When, naturally cool to room temperature, take out, final acquisition has nucleocapsid structure Li1.1V0.9O2/ C micro-sphere compound anode material.
The preparation of above-mentioned composite negative pole material electrode and performance test are same as Example 1, electrochemical property test result
It is shown in Table 1.
Embodiment 5
There is the Li of nucleocapsid structure1.1V0.9O2The preparation method of/C micro-sphere compound anode material, comprises the following steps：
By synthesis material lithium vanadium mixture (LiOH, V2O3) and ethylene glycol in mass ratio be 80：20 weigh 40 grams of gross mass,
Lithium vanadium mixture is Li：V mol ratio 1.1：0.9 LiOH, V2O332 grams of mixture, is dissolved in 40 milliliters of dehydrated alcohol, and adds
8 grams of ethylene glycol, makes reactant be fully dispersed in ethanol, with 260 revs/min of rotating speed ball milling 4 hours on planetary ball mill
After obtain colloidal mixture, colloidal mixture is put in open glass ware, 60 DEG C evaporation dry 48 hours after obtain presoma.
Then by this presoma in argon gas atmosphere 400 DEG C of carbonizations of low temperature 5 hours, then synthesize 6 hours at 1050 DEG C of high temperature, naturally cold
But arrive room temperature, take out, final acquisition has nucleocapsid structure Li1.1V0.9O2/ C micro-sphere compound anode material.
The preparation of above-mentioned composite negative pole material electrode and performance test are same as Example 1, electrochemical property test result
It is shown in Table 1.
Embodiment 6
There is the Li of nucleocapsid structure1.1V0.9O2The preparation method of/C micro-sphere compound anode material, comprises the following steps：
By synthesis material lithium vanadium mixture (LiNO3、V2O3) and polyvinyl alcohol in mass ratio be 80：20 weigh gross mass 40
Gram, lithium vanadium mixture is Li：V mol ratio 1.1：0.9 LiNO3、V2O332 grams of mixture, is dissolved in 40 milliliters of dehydrated alcohol, and
Add 8 grams of polyvinyl alcohol, so that reactant is fully dispersed in ethanol, with 250 revs/min of rotating speed ball milling on planetary ball mill
Obtain colloidal mixture after 4 hours, colloidal mixture is put in open glass ware, before 50 DEG C of evaporations obtain after drying 48 hours
Drive body.Then by this presoma in argon gas atmosphere 500 DEG C of carbonizations of low temperature 4 hours, then synthesize 7 hours at 1050 DEG C of high temperature,
Naturally cool to room temperature, take out, final acquisition has nucleocapsid structure Li1.1V0.9O2/ C micro-sphere compound anode material.
The preparation of electrode and performance test are same as Example 1, and electrochemical property test the results are shown in Table 1.
Embodiment 7
There is the Li of nucleocapsid structure1.1V0.9O2The preparation method of/C micro-sphere compound anode material, comprises the following steps：
By synthesis material lithium vanadium mixture (LiNO3、V2O5) and polyvinyl alcohol in mass ratio be 80：20 weigh gross mass 40
Gram, lithium vanadium mixture is Li：V mol ratio 1.1：0.9 LiNO3、V2O532 grams of mixture, is dissolved in 40 milliliters of dehydrated alcohol, and
Add 8 grams of polyvinyl alcohol, so that reactant is fully dispersed in ethanol, with 300 revs/min of rotating speed ball milling on planetary ball mill
Obtain colloidal mixture after 4 hours, colloidal mixture is put in open glass ware, before 80 DEG C of evaporations obtain after drying 36 hours
Drive body.Then by this presoma in argon gas atmosphere 500 DEG C of carbonizations of low temperature 4 hours, then synthesize 7 hours at 1050 DEG C of high temperature,
Naturally cool to room temperature, take out, final acquisition has nucleocapsid structure Li1.1V0.9O2/ C micro-sphere compound anode material.
The preparation of electrode and performance test are same as Example 1, and electrochemical property test the results are shown in Table 1.
Embodiment 8
There is the Li of nucleocapsid structure1.1V0.9O2The preparation method of/C micro-sphere compound anode material, comprises the following steps：
By synthesis material lithium vanadium mixture (Li2C2O4、V2O5) and polyvinyl alcohol in mass ratio be 80：20 weigh gross mass 40
Gram, lithium vanadium mixture is Li：V mol ratio 1.1：0.9 Li2C2O4、V2O532 grams of mixture, is dissolved in 40 milliliters of dehydrated alcohol,
And add 8 grams of polyvinyl alcohol, so that reactant is fully dispersed in ethanol, with 300 revs/min of rotating speed ball on planetary ball mill
Mill obtained colloidal mixture after 4 hours, and colloidal mixture is put in open glass ware, and 80 DEG C of evaporations obtain after drying 36 hours
Presoma.Then by this presoma in argon gas atmosphere 500 DEG C of carbonizations of low temperature 3 hours, then synthesis 8 is little at 1050 DEG C of high temperature
When, naturally cool to room temperature, take out, final acquisition has nucleocapsid structure Li1.1V0.9O2/ C micro-sphere compound anode material.
The preparation of electrode and performance test are same as Example 1, and electrochemical property test the results are shown in Table 1.
Comparative example 1
By synthesis material lithium vanadium mixture (Li2CO3、V2O3) and acetylene black in mass ratio be 80：20 weigh gross mass 40
Gram, lithium vanadium mixture is Li：V mol ratio 1.1：0.9 Li2CO3、V2O332 grams of mixture, is scattered in 40 milliliters of dehydrated alcohol
In, on planetary ball mill with 300 revs/min of rotating speed ball milling 4 hours after, said mixture is put in open glass ware,
80 DEG C of evaporations obtain presoma after drying 36 hours.Then by this presoma in argon gas atmosphere 600 DEG C of carbonizations of low temperature 2 hours,
Synthesize 10 hours at 1050 DEG C of high temperature again, naturally cool to room temperature, take out, finally obtain Li1.1V0.9O2/ C composite negative pole material
Material.
The preparation of electrode and performance test are same as Example 1, and electrochemical property test the results are shown in Table 1.
Table 1 has the Li of nucleocapsid structure1.1V0.9O2The chemical property of/C micro-sphere compound anode material
Claims (10)
1. a kind of Li with nucleocapsid structure1.1V0.9O2/ C micro-sphere compound anode material is it is characterised in that described composite negative pole material
Material is with Li1.1V0.9O2Microsphere is nucleome；Shell, with amorphous carbon as matrix, is uniformly distributed and embedded into nanometer in described matrix
Li1.1V0.9O2Granule.
2. there is the Li of nucleocapsid structure according to claim 11.1V0.9O2/ C micro-sphere compound anode material it is characterised in that with
Finally the gross weight of composite negative pole material to be obtained is standard, Li1.1V0.9O2Content be 90～99.9 weight %, amorphous
The content of carbon is 0.1～10 weight %.
3. there is the Li of nucleocapsid structure according to claim 11.1V0.9O2/ C micro-sphere compound anode material is it is characterised in that institute
State Li1.1V0.9O2A diameter of 0.5～2 μm of microsphere, shell thickness is 100～150nm, described Li1.1V0.9O2The particle diameter of/C microsphere
For 0.7～2.5 μm.
4. there is the Li of nucleocapsid structure according to claim 11.1V0.9O2/ C micro-sphere compound anode material is it is characterised in that institute
State amorphous carbon and there is nanometer Li described in meso-hole structure1.1V0.9O2The particle diameter of granule is 30～50nm.
5. there is described in a kind of Claims 1 to 4 any one the Li of nucleocapsid structure1.1V0.9O2/ C micro-sphere compound anode material
Preparation method is it is characterised in that comprise the following steps：Will be by element Li：The mol ratio of V is 1.1:0.9 lithium source and vanadium source, with
And in adjuvant, be then ground；It is put into grinding the colloidal mixture taking-up obtaining in open-top receptacle, be evaporated drying
After obtain presoma；Described presoma is carried out low-temperature carbonization, high-temperature nuclei in inertia or reducing atmosphere successively, obtains institute
State the Li with nucleocapsid structure1.1V0.9O2/ C micro-sphere compound anode material.
6. there is the Li of nucleocapsid structure according to claim 51.1V0.9O2The preparation method of/C micro-sphere compound anode material, its
It is characterised by, described lithium source is Li2CO3、LiNO3、CH3COOLi、LiOH、Li2C2O4One or more of；Described vanadium source is
VO2、V2O3、V2O5、V4O7、NH4VO3One or more of.
7. there is the Li of nucleocapsid structure according to claim 51.1V0.9O2The preparation method of/C micro-sphere compound anode material, its
It is characterised by, described adjuvant is polyvinyl alcohol, ethylene glycol, Polyethylene Glycol, citric acid, glucose, sucrose, glycerol, epoxy
One or more of resin.
8. there is the Li of nucleocapsid structure according to claim 51.1V0.9O2The preparation method of/C micro-sphere compound anode material, its
Be characterised by, described be ground to ball milling, ball milling jitter time be 2～4h, rotating speed be 250～300r/min.
9. there is the Li of nucleocapsid structure according to claim 51.1V0.9O2The preparation method of/C micro-sphere compound anode material, its
It is characterised by, at 50 DEG C～90 DEG C, evaporation time is 24～48h to the temperature control of evaporation；The temperature control of described low-temperature carbonization
At 400 DEG C～600 DEG C, carbonization time is 2～5h；The temperature control of described high-temperature nuclei at 950 DEG C～1100 DEG C, the response time
For 6～12h.
10. there is described in a kind of Claims 1 to 4 any one the Li of nucleocapsid structure1.1V0.9O2/ C micro-sphere compound anode material exists
Application in preparation battery cathode.
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